CN109467242B - Circuit board comprehensive wastewater treatment and copper recovery process capable of saving alkali consumption - Google Patents
Circuit board comprehensive wastewater treatment and copper recovery process capable of saving alkali consumption Download PDFInfo
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 13
- 239000003513 alkali Substances 0.000 title claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 10
- 239000010949 copper Substances 0.000 title claims abstract description 10
- 238000011084 recovery Methods 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004458 analytical method Methods 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 11
- 238000011069 regeneration method Methods 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 230000003311 flocculating effect Effects 0.000 claims abstract 2
- 239000002351 wastewater Substances 0.000 claims description 88
- 239000012528 membrane Substances 0.000 claims description 59
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 43
- 229910001431 copper ion Inorganic materials 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 19
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 19
- 238000005189 flocculation Methods 0.000 claims description 19
- 230000016615 flocculation Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 15
- 238000005374 membrane filtration Methods 0.000 claims description 13
- 239000010802 sludge Substances 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/22—Treatment of water, waste water, or sewage by freezing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a circuit board comprehensive wastewater treatment and copper recovery process capable of saving alkali consumption, which comprises the following steps: s1, preprocessing; s2, special film treatment; s3, recycling reclaimed water. S4, resin adsorption; s5, resin analysis and regeneration; s6, oxidizing S7: flocculating and settling; s8, discharging after reaching the standard. The invention reduces the cost of the circuit board wastewater treatment and realizes the recycling of resources.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a comprehensive wastewater treatment and copper recovery process for a circuit board, which saves the alkali consumption.
Background
In the production process of the circuit board, a large amount of brushing wastewater, general washing wastewater, organic wastewater, comprehensive wastewater, nickel-containing wastewater, silver-containing wastewater, cyanide-containing wastewater, demolding development wastewater and the like can be generated, the wastewater cannot be directly discharged, and the wastewater can be treated to meet the discharge requirement, but the conventional wastewater treatment process is complex, the treatment cost is high, the sludge generation and multiprocessing cost is high, and the resources cannot be recovered.
Disclosure of Invention
Based on the above, it is necessary to provide a process for treating integrated wastewater of circuit board and recovering copper, which saves alkali consumption, comprising the following steps:
s1, pretreatment: discharging the wastewater into a pretreatment system, and pretreating the wastewater to remove particulate matters and impurities in the wastewater;
s2, special film treatment: the pretreated wastewater enters a special membrane filtration system, and colloid and suspended matters in the wastewater are filtered by using a special separation membrane in the special membrane filtration system;
s3, recycling reclaimed water: the wastewater after the special membrane treatment enters a special membrane system, and concentrated water and reclaimed water are obtained after the treatment of the special membrane system, wherein the concentrated water enters a pretreatment system, and the reclaimed water can be used for production water.
S4, resin adsorption: the wastewater treated by the special membrane enters a special resin adsorption system, and the ion exchange resin in the special resin adsorption system is used for adsorbing copper ions in the wastewater, so that the copper ions in the wastewater are removed;
s5, resin analysis and regeneration:
s5.1: the method comprises the steps of performing analysis and regeneration treatment on the ion exchange resin with saturated adsorption by using sulfuric acid, so that copper ions adsorbed in the ion exchange resin are analyzed, and the copper ions enter sulfuric acid to obtain resin analysis liquid;
s5.2, the resin analysis liquid enters a special membrane concentration system, and the special concentration membrane is used for filtering the resin analysis liquid to further concentrate the concentration of copper ions, so as to obtain concentrated liquid and permeate liquid;
wherein the concentrated solution is resin analysis solution which is filtered by the special concentrated film and remains most copper ions, and the permeate solution is resin analysis solution which is transmitted by the special concentrated film and has extremely low copper ion content.
S5.3: the concentrated solution enters a freezing crystallization system, and the temperature of the concentrated solution is reduced, so that the solubility of copper sulfate in the concentrated solution is reduced, and anhydrous copper sulfate crystals are separated out, so that the copper sulfate is recovered.
S6, oxidizing: the wastewater subjected to resin adsorption treatment enters a fluidized bed Fenton system to perform advanced oxidation reaction, so that COD in the wastewater is reduced;
s7: flocculation precipitation: the wastewater after the oxidation reaction enters a flocculation sedimentation tank in a coagulation sedimentation system, ferrous sulfate and caustic soda are added into the flocculation sedimentation tank, and copper ions in the wastewater are precipitated to obtain sludge;
s8, standard emission: and discharging the supernatant meeting the discharge standard after the wastewater is precipitated.
The pretreatment is a wastewater treatment process in the prior art, and the pretreatment of wastewater can effectively reduce the fouling, scaling and membrane degradation of the wastewater in the process treatment process, so that the system efficiency is greatly improved, and the optimization of the water yield, the recovery rate and the running cost of the system is realized.
The COD of the wastewater can be effectively reduced by the oxidation treatment, so that the consumption of alkali in the subsequent flocculation and precipitation process can be effectively reduced.
Preferably, the special separation membrane of the special membrane filtration system is an ultrafiltration membrane made of PAN.
The ultrafiltration membrane is a microporous filtration membrane with consistent pore size and rated pore size range below 0.01 micrometer. Solute molecules smaller than the pore size can be screened out by applying appropriate pressure on one side of the membrane to separate particles with molecular weight greater than 500 daltons (atomic mass units) and particle size greater than 10 nanometers.
Preferably, the special separation membrane of the special membrane system is an RO membrane.
The pore size of the RO membrane is 0.0001 microns, and the bacteria and viruses are 5000 times of the RO membrane, so that only water molecules and partial mineral ions can pass through (the passing ions are oriented without beneficial loss), and other impurities and heavy metals cannot pass through.
Preferably, the special concentrating membrane is an NF membrane.
NF membrane has a molecular weight cut-off between RO and UF of 200-2000, and the surface separation layer of NF has a microporous structure of about 1 nm.
Preferably, the special separation membrane of the special membrane system is a three-layer composite membrane, and the thickness of the filtering cortex is 0.2 mu m.
Preferably, in step S6, the method further comprises accelerating the fluidized bed reaction efficiency by inducing formation of coal crystals.
Preferably, in step S7, the amounts of ferrous sulfate and caustic soda added are such that the amount of copper ions in the wastewater is less than 0.5mg/L.
The amount of ferrous sulfate and caustic soda added is preferably such that the copper ion content in the wastewater is less than 0.5mg/L.
Preferably, in the step S7, the method further includes a step of performing filter pressing treatment on the sludge precipitated in the flocculation precipitation tank and discharging the sludge.
According to the invention, copper ions are recycled before Xu Ning precipitation, so that a large amount of copper ions are recycled, and the sludge yield is reduced by 70% -80% compared with that of the traditional treatment process.
The principle and effect of the present invention are further described below with reference to the above technical schemes:
according to the invention, special resin is used for adsorbing copper ions, a special film concentration system is used for further concentrating copper ions, an anhydrous copper sulfate product is obtained through a freezing crystallization technology, the sludge quantity is reduced by 70-80% compared with that of the traditional treatment process, and the reclaimed water of the special film system can be recycled to a production line, so that the recycling of resources is realized, the cost of circuit board wastewater treatment is reduced, and the COD in the circuit board wastewater can be effectively removed by adopting a fluidized bed Fenton system.
Drawings
FIG. 1 is a process flow diagram of a circuit board integrated wastewater treatment and copper recovery process for saving alkali consumption according to an embodiment of the invention.
Detailed Description
For the convenience of understanding by those skilled in the art, the present invention will be described in further detail with reference to the following examples:
all the devices mentioned in the invention are devices of the prior art and are available on the market.
Example 1
A circuit board comprehensive wastewater treatment and copper recovery process capable of saving alkali consumption comprises the following steps:
s1, pretreatment: discharging the wastewater into a pretreatment system, and pretreating the wastewater to remove particulate matters and impurities in the wastewater;
s2, special film treatment: the pretreated wastewater enters a special membrane filtration system, and colloid and suspended matters in the wastewater are filtered by using a special separation membrane in the special membrane filtration system;
s3, recycling reclaimed water: the wastewater after the special membrane treatment enters a special membrane system, and concentrated water and reclaimed water are obtained after the treatment of the special membrane system, wherein the concentrated water enters a pretreatment system, and the reclaimed water can be used for production water.
S4, resin adsorption: the wastewater treated by the special membrane enters a special resin adsorption system, and the ion exchange resin in the special resin adsorption system is used for adsorbing copper ions in the wastewater, so that the copper ions in the wastewater are removed;
s5, resin analysis and regeneration:
s5.1: the method comprises the steps of (1) carrying out analysis and regeneration treatment on the ion exchange resin with saturated adsorption by sulfuric acid, so that copper ions adsorbed in the ion exchange resin are analyzed, and enter sulfuric acid to obtain resin analysis liquid, wherein the concentration of the copper ions in the resin analysis liquid can reach 20-30g/L;
s5.2, the resin analysis liquid enters a special film concentration system, the special concentration film is used for filtering the resin analysis liquid, so that the concentration of copper ions is further concentrated to obtain concentrated liquid and permeate liquid, and the copper ions in the concentrated liquid can reach 60-80 g/L;
s5.3: the concentrated solution enters a freezing crystallization system, the temperature of the concentrated solution is reduced, so that the solubility of copper sulfate in the concentrated solution is reduced, and anhydrous copper sulfate crystals are separated out to recover copper sulfate, wherein the purity of the prepared anhydrous copper sulfate crystals can reach more than 99 percent.
S6, oxidizing: the wastewater subjected to resin adsorption treatment enters a fluidized bed Fenton system to perform advanced oxidation reaction, so that COD in the wastewater is reduced, and the COD removal rate can reach 88%;
s7: flocculation precipitation: the wastewater after the oxidation reaction enters a flocculation sedimentation tank in a coagulation sedimentation system, ferrous sulfate and caustic soda are added into the flocculation sedimentation tank, and copper ions in the wastewater are precipitated to obtain sludge;
s8, standard emission: and discharging the supernatant meeting the discharge standard after the wastewater is precipitated.
Example 2
A circuit board comprehensive wastewater treatment and copper recovery process capable of saving alkali consumption comprises the following steps:
s1, pretreatment: discharging the wastewater into a pretreatment system, and pretreating the wastewater to remove particulate matters and impurities in the wastewater;
s2, special film treatment: the pretreated wastewater enters a special membrane filtration system, and an ultrafiltration membrane in the special membrane filtration system is used for filtering colloid and suspended matters in the wastewater;
s3, recycling reclaimed water: the wastewater after the special membrane treatment enters a special membrane system, and concentrated water and reclaimed water are obtained after RO membrane filtration treatment in the special membrane system, wherein the concentrated water enters a pretreatment system, and the reclaimed water can be used for production water.
S4, resin adsorption: the wastewater treated by the special membrane enters a special resin adsorption system, and the ion exchange resin in the special resin adsorption system is used for adsorbing copper ions in the wastewater, so that the copper ions in the wastewater are removed;
s5, resin analysis and regeneration:
s5.1: the method comprises the steps of (1) carrying out analysis and regeneration treatment on the ion exchange resin with saturated adsorption by sulfuric acid, so that copper ions adsorbed in the ion exchange resin are analyzed, and enter sulfuric acid to obtain resin analysis liquid, wherein the concentration of the copper ions in the resin analysis liquid can reach 20-30g/L;
s5.2, the resin analysis liquid enters a special membrane concentration system, and is filtered by using an NF membrane, so that the concentration of copper ions is further concentrated to obtain concentrated solution and permeate liquid, wherein the copper ions in the concentrated solution can reach 60-80 g/L;
s5.3: the concentrated solution enters a freezing crystallization system, the temperature of the concentrated solution is reduced, so that the solubility of copper sulfate in the concentrated solution is reduced, and anhydrous copper sulfate crystals are separated out to recover copper sulfate, wherein the purity of the prepared anhydrous copper sulfate crystals can reach more than 99 percent.
S6, oxidizing: the wastewater subjected to resin adsorption treatment enters a fluidized bed Fenton system to perform advanced oxidation reaction, so that COD in the wastewater is reduced, and the COD removal rate can reach 88%;
s7: flocculation precipitation: the wastewater after the oxidation reaction enters a flocculation sedimentation tank in a coagulation sedimentation system, ferrous sulfate and caustic soda are added into the flocculation sedimentation tank, and copper ions in the wastewater are precipitated to obtain sludge;
s8, standard emission: and discharging the supernatant meeting the discharge standard after the wastewater is precipitated.
Example 3
A circuit board comprehensive wastewater treatment and copper recovery process capable of saving alkali consumption comprises the following steps:
s1, pretreatment: discharging the wastewater into a pretreatment system, and pretreating the wastewater to remove particulate matters and impurities in the wastewater;
s2, special film treatment: the pretreated wastewater enters a special membrane filtration system, and an ultrafiltration membrane in the special membrane filtration system is used for filtering colloid and suspended matters in the wastewater;
s3, recycling reclaimed water: the wastewater after the special membrane treatment enters a special membrane system, and concentrated water and reclaimed water are obtained after RO membrane filtration treatment in the special membrane system, wherein the concentrated water enters a pretreatment system, and the reclaimed water can be used for production water.
S4, resin adsorption: the wastewater treated by the special membrane enters a special resin adsorption system, and the ion exchange resin in the special resin adsorption system is used for adsorbing copper ions in the wastewater, so that the copper ions in the wastewater are removed;
s5, resin analysis and regeneration:
s5.1: the method comprises the steps of (1) carrying out analysis and regeneration treatment on the ion exchange resin with saturated adsorption by sulfuric acid, so that copper ions adsorbed in the ion exchange resin are analyzed, and enter sulfuric acid to obtain resin analysis liquid, wherein the concentration of the copper ions in the resin analysis liquid can reach 20-30g/L;
s5.2, the resin analysis liquid enters a special membrane concentration system, and is filtered by using an NF membrane, so that the concentration of copper ions is further concentrated to obtain concentrated solution and permeate liquid, wherein the copper ions in the concentrated solution can reach 60-80 g/L;
s5.3: the concentrated solution enters a freezing crystallization system, the temperature of the concentrated solution is reduced, so that the solubility of copper sulfate in the concentrated solution is reduced, and anhydrous copper sulfate crystals are separated out to recover copper sulfate, wherein the purity of the prepared anhydrous copper sulfate crystals can reach more than 99 percent.
S6, oxidizing: the wastewater subjected to resin adsorption treatment enters a fluidized bed Fenton system to perform advanced oxidation reaction, so that COD in the wastewater is reduced, and coal-promoting crystallization is induced to be formed, so that the reaction efficiency of the fluidized bed is accelerated, wherein the removal rate of the COD can reach 88%;
s7: flocculation precipitation: the wastewater after the oxidation reaction enters a flocculation sedimentation tank in a flocculation sedimentation system, ferrous sulfate and caustic soda are added into the flocculation sedimentation tank, the ferrous sulfate and the caustic soda react with copper ions and are precipitated to obtain sludge, the amount of the added ferrous sulfate and caustic soda is such that the copper ions in the wastewater are less than 0.5mg/L, and then the sludge precipitated in the flocculation sedimentation tank is subjected to filter pressing treatment and discharged.
S8, standard emission: and discharging the supernatant meeting the discharge standard after the wastewater is precipitated.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (1)
1. The comprehensive wastewater treatment and copper recovery process for the circuit board capable of saving the alkali consumption is characterized by comprising the following steps of: s1, pretreatment: discharging the wastewater into a pretreatment system, and pretreating the wastewater to remove particulate matters and impurities in the wastewater;
s2, special film treatment: the pretreated wastewater enters a special membrane filtration system, and colloid and suspended matters in the wastewater are filtered by using a special separation membrane in the special membrane filtration system;
s3, recycling reclaimed water: the wastewater after the special membrane treatment enters a special membrane system, and concentrated water and reclaimed water are obtained after the treatment of the special membrane system, wherein the concentrated water enters a pretreatment system, and the reclaimed water can be used for production water;
s4, resin adsorption: the wastewater treated by the special membrane enters a special resin adsorption system, and the ion exchange resin in the special resin adsorption system is used for adsorbing copper ions in the wastewater, so that the copper ions in the wastewater are removed;
s5, resin analysis and regeneration:
s5.1: the method comprises the steps of performing analysis and regeneration treatment on the ion exchange resin with saturated adsorption by using sulfuric acid, so that copper ions adsorbed in the ion exchange resin are analyzed, and the copper ions enter sulfuric acid to obtain resin analysis liquid;
s5.2, the resin analysis liquid enters a special membrane concentration system, and the special concentration membrane is used for filtering the resin analysis liquid to further concentrate the concentration of copper ions, so as to obtain concentrated liquid and permeate liquid;
s5.3: the concentrated solution enters a freezing crystallization system, and the temperature of the concentrated solution is reduced, so that the solubility of copper sulfate in the concentrated solution is reduced, and anhydrous copper sulfate crystals are separated out to recover copper sulfate;
s6, oxidizing: the wastewater subjected to resin adsorption treatment enters a fluidized bed Fenton system to perform advanced oxidation reaction, so that COD in the wastewater is reduced;
s7, flocculating and precipitating: the wastewater after the oxidation reaction enters a flocculation sedimentation tank in a coagulation sedimentation system, ferrous sulfate and caustic soda are added into the flocculation sedimentation tank, and copper ions in the wastewater are precipitated to obtain sludge;
s8, standard emission: discharging the supernatant which is obtained after the wastewater is precipitated and meets the discharge standard;
the special separation membrane of the special membrane system is an RO membrane;
the special concentration membrane is an NF membrane, the interception molecular weight of the NF membrane is between RO and UF and is 200-2000, and the surface separation layer of the NF has a microporous structure of about 1 nm;
the special separation membrane of the special membrane system is a three-layer composite membrane, and the thickness of the filtering cortex is 0.2 mu m;
in step S6, the method further comprises the step of accelerating the reaction efficiency of the fluidized bed by inducing the formation of coal-promoting crystals;
in the step S7, the amount of the added ferrous sulfate and caustic soda is such that the copper ion amount in the wastewater is less than 0.5mg/L;
in the step S7, the method also comprises the step of carrying out filter pressing treatment on the sludge precipitated in the flocculation precipitation tank and discharging the sludge.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863530A (en) * | 2010-07-07 | 2010-10-20 | 南京大学 | Continuous advanced treatment system and treatment method for tail water containing heavy metal ions |
| CN102795723A (en) * | 2012-08-15 | 2012-11-28 | 广东达志环保科技股份有限公司 | Resource recovery method of acidic copper-containing waste solution |
| CN108002595A (en) * | 2017-12-22 | 2018-05-08 | 星华科技（惠州）有限公司 | A kind of wiring board comprehensive effluent disposal technology |
| CN108609758A (en) * | 2018-04-02 | 2018-10-02 | 广东世来福环保科技有限公司 | PCB circuit board comprehensive wastewater handles sludge decrement process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010046562A (en) * | 2008-08-19 | 2010-03-04 | En-Tec Co Ltd | Resource recovery type water treatment method and system |
-
2018
- 2018-10-29 CN CN201811265007.0A patent/CN109467242B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863530A (en) * | 2010-07-07 | 2010-10-20 | 南京大学 | Continuous advanced treatment system and treatment method for tail water containing heavy metal ions |
| CN102795723A (en) * | 2012-08-15 | 2012-11-28 | 广东达志环保科技股份有限公司 | Resource recovery method of acidic copper-containing waste solution |
| CN108002595A (en) * | 2017-12-22 | 2018-05-08 | 星华科技（惠州）有限公司 | A kind of wiring board comprehensive effluent disposal technology |
| CN108609758A (en) * | 2018-04-02 | 2018-10-02 | 广东世来福环保科技有限公司 | PCB circuit board comprehensive wastewater handles sludge decrement process |
Non-Patent Citations (5)
| Title |
|---|
| 中国环境保护产业协会.国家重点环境保护实用技术及示范工程汇编 2014版.《国家重点环境保护实用技术及示范工程汇编 2014版》.中国环境出版社,2015,第196页. * |
| 曾桂生等.砷碱渣中物质的结晶与分离.《砷碱渣中物质的结晶与分离》.冶金工业出版社,2016,第59页. * |
| 王国建等.功能高分子材料.《功能高分子材料》.同济大学出版社,2010,第92页. * |
| 邓巍.云铜股份志 1958-2006.《云铜股份志 1958-2006》.云南铜业股份有限公司,2006,第328页. * |
| 郭宇杰等.工业废水处理工程.《工业废水处理工程》.华东理工大学出版社,2016,第118页. * |
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